Catalysts for olefin polymerization

ABSTRACT

Selected nickel complexes of the anions of certain 2-aminotropones are olefin polymerization catalysts. Novel 2-aminotropones and their nickel complexes are also disclosed together with methods of making these 2-aminotropones.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority under 35 U.S.C. §119 from U.S.Provisional Application Ser. No. 60/161,237 (filed Oct. 22, 1999), whichis incorporated by reference herein for all purposes as if fully setforth.

FIELD OF THE INVENTION

[0002] This invention concerns new processes for the polymerization ofolefins using as a polymerization catalyst a nickel complex of certain2-aminotropones. Also described are novel compounds that are thecomplexes and intermediates for making the complexes, as well asprocesses for producing such compounds.

TECHNICAL BACKGROUND

[0003] Polymers of ethylene and other olefins are important items ofcommerce, and these polymers are used in a myriad of ways, from lowmolecular weight polyolefins being used as a lubricant and in waxes, tohigher molecular weight grades being used for fiber, films, moldingresins, elastomers, etc. In most cases, olefins are polymerized using acatalyst, often a transition metal compound or complex. These catalystsvary in cost per unit weight of polymer produced, the structure of thepolymer produced, the possible need to remove the catalyst from thepolyolefin, the toxicity of the catalyst, etc. Due to the commercialimportance of polymerizing olefins, new polymerization catalysts areconstantly being sought.

[0004] Arylaminotropones are useful as chemical intermediates, forinstance in the synthesis of pharmaceuticals and pesticides.

[0005] Nickel complexes of various neutral ligands and monoanionicligands are known as catalysts for the polymerization of ethylene andother olefins, see for instance (for monoanionic ligands) U.S.6,060,569,W09830609 (corresponding to United States Patent Application Serial No.09/006536, filed Jan. 13, 1998) and W09842664, which are incorporated byreference herein for all purposes as if fully set forth. None of thesereferences describe the use of aminotropones as ligands for nickelcontaining olefin polymerization catalysts.

[0006] Anilinotropones, especially 2-anilinotropones, have been made bya variety of methods, see for instance K. Kikuchi, Bull. Chem. Soc.Jpn., vol. 51, p. 2338 (1978); T. Nozoe, Bull. Chem. Soc. Jpn., vol. 51,p. 2185 (1978); and W. R. Brasen, J. Am. Chem. Soc., vol. 83, p. 3125(1961). The methods described in these references are different from themethods described herein. In addition, yields of the desired2-anilinotropones are generally lower than reported herein, and/orsterically hindered less basic arylamines are not used in the synthesisthereof.

SUMMARY OF THE INVENTION

[0007] One aspect of the present invention concerns a first process forthe polymerization of olefins, comprising the step of contacting, at atemperature of about −100° C. to about +200° C., one or more olefinswith an active catalyst comprising a nickel complex of an anion of theformula

[0008] wherein:

[0009] R²is hydrocarbyl or substituted hydrocarbyl, provided that R² isattached to said nitrogen atom in (I) by an atom that has at least 2other atoms that are not hydrogen attached to it; and

[0010] R³, R⁴, R⁵, R6 and R⁷ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any two of R³, R⁴, R⁵, R⁶ and R⁷ vicinal to one another may form aring.

[0011] Another aspect of the present invention concerns a second processfor the polymerization of olefins, comprising the step of contacting, ata temperature of about −100° C. to about +200° C., one or more olefinswith a compound of the formula

[0012] wherein:

[0013] R² is hydrocarbyl or substituted hydrocarbyl, provided that R² isattached to said nitrogen atom in (I) by an atom that has at least 2other atoms that are not hydrogen attached to it;

[0014] R³, R⁴, R⁵, R⁶ and R⁷ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any two of R³, R⁴, R⁵, R⁶ and R⁷ vicinal to one another may form aring;

[0015] L¹ is a monodentate monoanionic ligand into which an olefinmolecule may insert between L¹ and the nickel atom, and L² is an emptycoordination site or a monodentate neutral ligand which may be displacedby an olef in, or L¹ and L² taken together are a monoanionic bidentateligand into which an olefin may insert between said monoanionicbidentate ligand and the nickel atom;

[0016] and provided that when L¹ and L² taken together are

[0017] then a cocatalyst is also present.

[0018] In the above-mentioned processes, (II) and/or the nickel complexof (I) may in and of themselves be active catalysts, or may be“activated” by contact with a cocatalyst/activator, as exemplified bythe case when L¹ and L² taken together are (I).

[0019] The present invention also concerns a compound of the formula

[0020] wherein:

[0021] R² is hydrocarbyl or substituted hydrocarbyl, provided that R² isattached to said nitrogen atom in (I) by an atom that has at least 2other atoms that are not hydrogen attached to it; and

[0022] R³, R⁴ , R⁵, R⁶ and R⁷ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any two of R³, R⁴, R⁵, R⁶ and R⁷ vicinal to one another may form aring;

[0023] L¹ is a monodentate monoanionic ligand, and L² is a monodentateneutral ligand or an empty coordination site, or L¹ and L² takentogether are a monoanionic bidentate ligand.

[0024] Another aspect of the present invention is a process for making2-arylamino substituted tropones, comprising the step of contacting, insolution at a temperature of about 20° C. to about 150° C., a firstcompound of the formula

[0025] a second compound of the formula HNR⁹R⁹ (IV), a palladiumcompound, a base capable of deprotonating said second compound, and athird compound which is a mono- or diphosphine in which all of the bondsto phosphorous are to carbon atoms, wherein:

[0026] R³, R⁴, R⁵, R⁶ and R⁷ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any two of R³, R⁴, R⁵, R⁶ and R⁷ vicinal to one another may form aring;

[0027] R⁸ is a group such that the conjugate acid of —OR⁸ has a pKa of<0 in water at 20° C.;

[0028] R¹⁹ is hydrocarbyl, substituted hydrocarbyl or hydrogen; and

[0029] R⁹ is aryl or substituted aryl.

[0030] Still another aspect of the present invention is a compound ofthe formula

[0031] wherein:

[0032] R³, R⁴, R⁵, R⁶ and R⁷ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any two of R³, R⁴, R⁵, R⁶ and R⁷ vicinal to one another may form aring; and

[0033] R¹¹, R ¹², R ¹³, R¹⁴ and R¹⁵ are each independently hydrogen,hydrocarbyl substituted hydrocarbyl or a functional group, provided thatany two of R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ vicinal to one another takentogether may form a ring; provided that:

[0034] both of R¹¹ and R¹⁵ are not hydrogen; and/or the total of theHammett a constants for R¹¹, R ², R¹³, R¹⁴ and R¹⁵ is about 0.50 ormore; and/or an E_(s) for one or both of R¹¹ and R¹⁵ is −0.10 or less.

[0035] A further aspect of the present invention is an anion of theformula

[0036] wherein:

[0037] R² is hydrocarbyl or substituted hydrocarbyl, provided that R² isattached to said nitrogen atom in (I) by an atom that has at least 2other atoms that are not hydrogen attached to it; and

[0038] R³, R⁴, R⁵, R⁶ and R⁷ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any two of R³, R⁴, R⁵, R⁶ and R⁷ vicinal to one another may form aring.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0039] Herein, certain terms are used. Some of them are:

[0040] A “hydrocarbyl group” is a univalent group containing only carbonand hydrogen. As examples of hydrocarbyls may be mentioned unsubstitutedalkyls, cycloalkyls and aryls. If not otherwise stated, it is preferredthat hydrocarbyl groups herein contain 1 to about 30 carbon atoms.

[0041] By “substituted hydrocarbyl” herein is meant a hydrocarbyl groupthat contains one or more substituent groups which are inert under theprocess conditions to which the compound containing these groups issubjected. The substituent groups also do not substantially interferewith the process. If not otherwise stated, it is preferred thatsubstituted hydrocarbyl groups herein contain 1 to about 30 carbonatoms. Included in the meaning of “substituted” are heteroaromaticrings. When a heteroaromatic ring is present, it may be attached toanother group through the heteroatom. In substituted hydrocarbyl all ofthe hydrogens may be substituted, as in trifluoromethyl.

[0042] By “(inert) functional group” herein is meant a group other thanhydrocarbyl or substituted hydrocarbyl which is inert under the processconditions to which the compound containing the group is subjected. Thefunctional groups also do not substantially interfere with any processdescribed herein that the compound in which they are present may takepart in. Examples of functional groups include halo (fluoro, chloro,bromo and iodo), ether such as —OR²² wherein R²² is hydrocarbyl orsubstituted hydrocarbyl. In cases in which the functional group may benear a nickel atom the functional group should not coordinate to themetal atom more strongly than the groups in those compounds are shown ascoordinating to the metal atom, that is they should not displace thedesired coordinating group.

[0043] By “olefin” is meant a compound containing one or more olefinicdouble bonds. In the event that the compound contains more than oneolefinic double bond, they should be non-conjugated. As examples ofolefins may be mentioned cyclopentene, a styrene, a norbornene, andcompounds of the formulas R¹⁷ CH═CH₂ wherein R¹⁷ is hydrogen or alkyl.

[0044] By an oligomerization or polymerization “co-catalyst” or“catalyst activator” is meant a compound that reacts with a transitionmetal compound to form an activated catalyst species. A preferredcatalyst activator is an “alkyl aluminum compound”, that is, a compoundwhich has at least one alkyl group bound to an aluminum atom. Othergroups such as alkoxide, hydride, and halogen may also be bound toaluminum atoms in the compound.

[0045] By “neutral Lewis base” is meant a compound, which is not an ion,that can act as a Lewis base. Examples of such compounds include ethers,amines, sulfides, and organic nitriles.

[0046] By “neutral Lewis acid” is meant a compound, which is not an ion,that can act as a Lewis acid. Examples of such compounds includeboranes, alkylaluminum compounds, aluminum halides, and antimony [V]halides.

[0047] By “cationic Lewis acid” is meant a cation that can act as aLewis acid. Examples of such cations are sodium and silver cations.

[0048] By an “empty coordination site” is meant a potential coordinationsite on a metal atom that does not have a ligand bound to it. Thus if anolefin molecule (such as an ethylene molecule) is in the proximity ofthe empty coordination site, the olefin molecule may coordinate to themetal atom.

[0049] By a “ligand into which an olefin molecule may insert” betweenthe ligand and a nickel atom is meant a ligand coordinated to the nickelatom into which an olefin molecule or a coordinated olefin molecule(such as an ethylene molecule or a coordinated ethylene molecule) mayinsert to start or continue a polymerization. For instance, this maytake the form of the reaction (wherein L is a ligand):

[0050] By a “ligand which may be displaced by an olefin” is meant aligand coordinated to a transition metal, which when exposed to anolefin (such as ethylene) is displaced as the ligand by the olefin.

[0051] By a “monoanionic ligand” is meant a ligand with one negativecharge.

[0052] By a “neutral ligand” is meant a ligand that is not charged.

[0053] “Alkyl group” and “substituted alkyl group” have their usualmeaning (see above for substituted under substituted hydrocarbyl).Unless otherwise stated, alkyl groups and substituted alkyl groupspreferably have 1 to about 30 carbon atoms.

[0054] By a “styrene” herein is meant a compound of the formula

[0055] wherein R⁴³ , R⁴⁴ , R⁴⁵ , R⁴⁶ and R⁴⁷ are each independentlyhydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group,all of which are inert in the polymerization process. It is preferredthat all of R⁴³, R⁴⁴, R⁴⁵, R⁴⁶ and R⁴⁷ are hydrogen. Styrene (itself) isa preferred styrene.

[0056] By a “norbornene” is meant ethylidene norbornene,dicyclopentadiene, or a compound of the formula

[0057] wherein R⁴⁰ is hydrogen or hydrocarbyl containing 1 to 20 carbonatoms. It is preferred that R⁴⁰ is hydrogen or alkyl, more preferablyhydrogen or n-alkyl, and especially preferably hydrogen. The norbornenemay be substituted by one or more hydrocarbyl, substituted hydrocarbylor functional groups in the R⁴⁰ or other positions, with the exceptionof the vinylic hydrogens, which remain. Norbornene (itself), dimethylendo-norbornene-2,3-dicarboxylate, t-butyl 5-norbornene-2-carobxylateare preferred norbornenes and norbornene (itself) is especiallypreferred.

[0058] By a “π-allyl group” is meant a monoanionic ligand with 3adjacent SP² carbon atoms bound to a metal center in an η³ fashion. Thethree SP² carbon atoms may be substituted with other hydrocarbyl groupsor functional groups.

[0059] By “aryl” is meant a monovalent aromatic group in which the freevalence is to the carbon atom of an aromatic ring. An aryl may have oneor more aromatic rings which may be fused, connected by single bonds orother groups.

[0060] By “substituted aryl” is meant a monovalent aromatic groupsubstituted as set forth in the above definition of “substitutedhydrocarbyl”. Similar to an aryl, a substituted aryl may have one ormore aromatic rings which may be fused, connected by single bonds orother groups; however, when the substituted aryl has a heteroaromaticring, the free valence in the substituted aryl group can be to aheteroatom (such as nitrogen) of the heteroaromatic ring instead of acarbon.

[0061] The polymerizations herein are carried out by a nickel complex ofanion (I). In (I), and in all complexes and compounds containing (I) orits parent conjugate acid, it is preferred that:

[0062] R³, R⁴, R⁵, R⁶ and R⁷ are all hydrogen; and/or R²is aryl orsubstituted aryl, especially phenyl or substituted phenyl.

[0063] Useful groups for R² include, for example

[0064] which may be substituted in any or all of their ring positions.It is preferred that at least one position next to (ortho) the freevalence of the aryl ring be substituted, and more preferred that both ofthese positions be substituted. In particular it is more preferred thatR² is

[0065] wherein each of R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are independentlyhydrogen, hydrocarbyl substituted hydrocarbyl or a functional group,provided that any two of R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ vicinal to oneanother taken together may form a ring. In one particularly preferredform both R¹¹ and R¹⁵ are not hydrogen, and/or R¹², R¹³ and R¹⁴ arehydrogen. In another preferred form R¹¹ and R¹⁵ are each independentlychosen from the group consisiting of alkyl containing 1 to 6 carbonatoms, perfluoroalkyl, alkoxy, phenyl and halo, more preferably alkylcontaining 1 to 4 carbon atoms, phenyl and halo. Particularly preferredare when R¹³and R¹³ are both ipropyl or phenyl, or when R¹¹ is methyland R¹⁵ is trifluoromethyl. Preferred specific groups (VI) are shown inTable 1. TABLE 1 R¹¹ R¹² R¹³ R¹⁴ R¹⁵ Me H H H Me IPr H H H iPr TBu H H HH TBu H H H Me Cl H H H Cl Br H H H Br F F F F F H CF₃ H CF₃ H Ph H H HPh F H H H F

[0066] All of the complexes of (I) can be made from the correspondingtropone

[0067] In turn (VII) can be made by the process described below, using apalladium catalyst in the presence of a phosphine compound.

[0068] In a process to make (VII) the appropriately substitutedarylamine, (IV) (and preferred substitution is the same as in (I)), isreacted with an appropriately substituted tropone ester (and preferredsubstitution is as in (I)), in the presence of a base, a palladiumcompound and a mono- or diphosphine. This reaction is carried out insolution, although not all of the ingredients must be totally soluble atall times, all of the starting materials, except the base, should be atleast somewhat soluble. Preferred solvents are relatively inert to allof the ingredients and products, and include hydrocarbon solvents suchas toluene, and ethers such as 1,4-dioxane, ethyl ether andtetrahydrofuran.

[0069] The palladium compound may be a Pd[II] compound or a Pd[0]compound, such as palladium acetate, PdX₂ wherein each X isindependently halogen, and palladium bis(dibenzylideneacetone), which ispreferred. The phosphine may be a mono- or diphosphine in which allthree of the bonds to phosphorous are to separate carbon atoms. It ispreferred that the phosphine be somewhat sterically hindered. Usefulphosphines include (o-tolyl)₃P, (t-Bu)₃P,1,1′-bis(diphenylphosphino)ferrocene,bis(2-diphenylphosphinophenyl)ether, 2-(di-t-butylphosphino)biphenyl,2-(dicylohexylphosphino)biphenyl, and

[0070] wherein each R¹⁰ is independently aryl or substituted aryl andpreferably all of R¹⁰ are phenyl (this compound is sometimes abbreviated“BINAP”). A preferred phosphine is (XI).

[0071] The base may be any metal salt, preferably an alkali metal salt,which can serve as an acceptor for the proton liberated from thearylamine during the process. The base should have at least sparingsolubility in the process solvent. Useful bases include alkali metalcarbonates such as cesium carbonate, alkali metal phosphates such aspotassium phosphate (K₃PO₄), alkali metal alkoxides such as potassiumt-butoxide, and alkali metal amides such as sodium hexamethyldisilamide.

[0072] In the process to make (VII) ratios of the various ingredientsare not critical, but to make efficient and economical use of thevarious ingredients, it is preferred that:

[0073] the molar ratio of (III):(IV) is about 0.1 to about 1.0, morepreferably about 0.8 to about 0.9;

[0074] the amount of gram-atoms of palladium (in whatever form the Pd isadded) is about 0.01 to about 10 percent of the number of moles oftropone, more preferably about 0.5 to 1.5 percent; and/or

[0075] the number of equivalents of base to moles of tropone ispreferably about 1.0 to about 4.0, more preferably about 1.2 to about1.6.

[0076] The process to make (VII) is preferably carried out at atemperature of about 20° C. to about 150° C., more preferably about 50°C. to about 120° C., and especially preferably about 70° C. to about 90°C. It is preferred to carry out the process in the absence of water (andother active hydrogen compounds) and oxygen, especially in the absenceof oxygen. This is conveniently carried done by carrying out the processunder an inert gas such as nitrogen or argon. The time required for thisprocess is also not critical, 3 to 48 hours, more typically 12-15 hours,being useful ranges.

[0077] In the process to make (VII), (III) is one of the startingmaterials. In (III), R⁸ is a group such that the conjugated acid of R⁸O-has a pKa of <0. Useful groups for R⁸ include R¹⁶SO₂-, wherein R¹⁶ isperfluorohydrocarbyl, especially perfluoroalkyl, and p-tolyl. Apreferred group for R⁸ is R¹⁶SO₂-, wherein R¹⁶ is perfluoroalkyl,especially trifluoromethyl (sometimes called the “triflate” group).(III) may be made by methods known in the art, for instance thepreparation of 2-triflatotropone is found in A. M. Echavarren, et al.,J. Am. Chem. Soc., vol. 110, p. 1557 (1988), which is included byreference herein.

[0078] The process to make (VII) (and hence (X)) herein produces thesetypes of compounds in improved yields and/or allows the production ofcompounds which cannot be produced by simple nucleophilic displacements,for instance using aromatic amines (IV) in which the amine group issterically hindered by substitution at one or both of the orthopositions, and/or the amine has reduced bascisity because the aromaticgroup bears electron withdrawing substituents.

[0079] In (IV) (and in any of the arylaminotropones subsequentlyproduced) it is preferred that R¹⁹ is alkyl, substituted alkyl orhydrogen, more preferred that it is alkyl or hydrogen, and especiallypreferred that it is hydrogen.

[0080] The steric effect of various groupings has been quantified by aparameter called Es, see R. W. Taft, Jr., J. Am. Chem. Soc., vol. 74, p.3120-3128 (1952), and M. S. Newman, Steric Effects in Organic Chemistry,John Wiley & Sons, New York, 1956, p. 598-603, both of which are herebyincorporated by reference herein for all purposes as if fully set forth.For the purposes herein, the Es values are those for o-substitutedbenzoates described in these publications. If the value for E_(s) forany particular group is not known, it can be determined by methodsdescribed in these publications. For the purposes herein, the value ofhydrogen is defined to be the same as for methyl (0.00). Representativevalues for E_(s) are (taken from Table V in Taft and Series 2-2 through2-10 in Newman) −OCH₃+0.97, −Br +0.01, -I −0.20, CH₃CH₂—0.07,CH₃CH₂CH₂—−0.36, i-C₃H₇—−0.47, t-C₄H₉—−1.54 C₆H₅—−0.90. In one preferredform of (X) the E_(s) for either of the ortho substituents is −0.10 orless, preferably about −0.25 or less, and especially preferably about−0.50 or less.

[0081] Another preferred form of (X) is when the phenyl ring haselectron withdrawing groups attached to it. The electron withdrawingability of various substituents may be measured by the Hammett constant,see for instance H. H. Jaffe, Chem. Rev., vol. 53, p. 191-261 (1953),especially Table 7, which is hereby included by reference. Since Hammettsubstituents constants are often not calculated for ortho substituents,for any ortho substituent the Hammett constant will be taken as theHammett para constant (apara). The total of all the σ constants for allof the substituents on the phenyl ring is about 0.50 or more, morepreferably about 0.75 or more.

[0082] It is also preferred in (I) (and in compounds in which it occurs)that provided that one or more of the following obtains: both of R¹¹ andR¹⁵ are not hydrogen; the total of the Hammett a constants for R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ is about 0.50 or more; and an E_(s) for one or bothof R¹¹ and R¹⁵ is −0.10 or less. The more preferred forms for (X) arealso preferred in (I).

[0083] Herein (VII) may be converted to a nickel complex such as (II),and in turn (II) may be active in and of itself and thus useful directlyas an olefin polymerization catalyst, or may be converted to an activepolymerization catalyst by contact with one or more other compounds(so-called cocatalysts). hus (VII) may be converted to its anion byreaction with a strong base such as sodium hydride, and this anion(which is actually (I)) may be reacted with an appropriate nickelcompound to form (II). Useful nickel compounds include:

[0084] (Ph₃P)₂Ni(Ph)(Cl) (see Example 13) which gives (II) in which L¹is Ph, and L² is Ph₃P;

[0085] (TMEDA)₂Ni(Ph)(Cl) in the presence of a “trapping ligand” L² suchas pyridine, which specifically gives (IX) for instance in which L¹ isPh, and L² is pyridine;

[0086] (Ph₃P)₂NiCl₂ which gives (II) in which L¹ is Cl, and L² is Ph₃P;and

[0087] ((allyl)Ni(X))₂ which gives (II) in which L¹ and L² takentogether are n-allyl.

[0088] Methods of synthesis of these types of nickel complexes may alsobe found in previously incorporated US6060569, W098/30609 andW098/42664, and R. H. Grubbs., et al., Organometallics, vol. 17, p. 3149(1988), which is also incorporated by reference herein for all purposesas if fully set forth.

[0089] In (II) useful groups L¹ include halide (especially chloride),hydrocarbyl and substituted hydrocarbyl especially phenyl and alkyl andparticularly phenyl, methyl, hydride and acyl. Useful groups for L²include phosphine such as triphenylphosphine, nitrile such asacetonitrile, ethers such as ethyl ether, pyridine, and tertiaryalkylamines such as TMEDA (N,N,N′,N′-tetramethyl-1,2-ethylenediamine).Alternatively L¹ and L² taken together may be a n-allyl or n-benzylgroup such as

[0090] wherein R is hydrocarbyl.

[0091] In (II) when an olefin (such as ethylene) may insert between L¹and the nickel atom, and L² is an empty coordination site or is a ligandwhich may be displaced by an olefin (such as ethylene), or L¹ and L²taken together are a bidentate monoanionic ligand into which an olefin(such as ethylene) may be inserted between that ligand and the nickelatom, (II) may by itself catalyze the polymerization of an olefin.Examples of L¹ into which an olefin (and particularly ethylene) mayinsert between it an the nickel atom are hydrocarbyl and substitutedhydrocarbyl especially phenyl and alkyl and particularly methyl, hydrideand acyl, and ligands L² which an olefin (and particularly ethylene) maydisplace include phosphine such as triphenylphosphine, nitrile such asacetonitrile, ether such as ethyl ether, pyridine, and tertiaryalkylamines such as TMEDA. Ligands in which L¹ and L² taken together area bidentate monoanionic ligand into which an olefin (and particularlyethylene) may insert between that ligand and the nickel atom includen-allyl or π-benzyl-type ligands (in this instance, sometimes it may benecessary to add a neutral Lewis acid cocatalyst such as triphenylboraneto initiate the polymerization, see for instance previously incorporatedW098/30609). For a summary of which ligands an olefin (and particularlyethylene) may insert into (between) the ligand and nickel atom) see forinstance J. P. Collman, et al., Principles and Applications ofOrganotransition Metal Chemistry, University Science Book, Mill Valley,Calif., 1987, included herein by reference. If for instance L¹ is not aligand into which an olefin (such as ethylene) may insert between it andthe nickel atom, it may be possible to add a cocatalyst which mayconvert L¹ into a ligand which will undergo such an insertion. Thus ifL¹ is halo such as chloride or bromide, or carboxylate, it may beconverted to hydrocarbyl such as alkyl by use of a suitable alkylatingagent such as an alkyla-luminum compound, a Grignard reagent or analkyllithium compound. It may be converted to hydride by used of acompound such as sodium borohydride.

[0092] In (II) when L¹ and L² taken together are (I), in thepolymerizations a cocatalyst (sometimes also called an activator) whichis an alkylating or hydriding agent is also present in the olefinpolymerization. It is preferred however that L¹ and L² taken togetherare not (I). A preferred cocatalyst is an alkylaluminum compound, andparticularly preferred are trialkylaluminum compound such astrimethylaluminum, triethylaluminum and tri-i-butylaluminum, andtrimethylaluminum is especially preferred. More than one such cocatalystmay be used in combination.

[0093] In the polymerizations herein homo- or copolymers of the variousolefins may be produced. A preferred olefin (or combination of olefins)is R¹⁷CH═CH₂ wherein R¹⁷ is hydrogen or n-alkyl containing 1 to 15carbon atoms, and especially preferred is when R¹⁷ is hydrogen or methyl(ethylene or propylene, respectively), and more preferred is when R¹⁷ ishydrogen (ethylene).

[0094] In the polymerization processes herein, the temperature at whichthe polymerization is carried out is about −100° C. to about +200° C.,preferably about −60° C. to about 150° C., more preferably about −20° C.to about 100° C. The pressure of the olefin (if it is a gas) at whichthe polymerization is carried out is not critical, atmospheric pressureto about 275 MPa being a suitable range. Generally speaking the responseof the catalyst, and hence the polymer produced, to the effects oftemperature and pressure are similar to other nickel catalysts, see forinstance US5880241 (incorporated by reference herein for all purposes asif fully set forth). As shown in Table 3 as the temperature increasescatalyst productivity increases until about 80° C. (at least under theseparticular polymerization conditions and this catalyst) and then startsdecreasing, and the branching level increases as the temperatureincreases. Up to a point at least, increasing the ethylene pressure(Table 4) increases catalyst productivity, decreases branching, andincreases polymer molecular weight. It is also believed that as theethylene pressure increases, it becomes more important that the ethyleneused be of high purity. The effect of catalyst loading (Table 5) issomewhat uncertain since in Example 54 there was a large exotherm.

[0095] The polymerization processes herein may be run in the presence ofvarious liquids, particularly aprotic organic liquids. The catalystsystem, monomer(s), and polymer may be soluble or insoluble in theseliquids, but obviously these liquids should not prevent thepolymerization from occurring Suitable liquids include alkanes,cycloalkanes, selected halogenated hydrocarbons and aromatichydrocarbons. Specific useful solvents include hexane, toluene, benzene,chlorobenzene, tetrahydrofuran, methylene chloride and1,2,4-trichlorobenzene. The effects of various solvents on thepolymerizations are shown in Table 7.

[0096] Various polar compounds such as ethyl acetate, triethylamine,water and ethanol may be present in the polymerization, although in someinstances the yields may be reduced (see Table 6). The polymerizationmay also be carried out in the presence of air. It is noted that thepolymerization proceeds with some of these additives even though theymay contain active hydrogen atoms (water, ethanol).

[0097] The olefin polymerizations herein may also initially be carriedout in the “solid state” by, for instance, supporting the nickelcompound on a substrate such as silica or alumina, activating ifnecessary it with one or more cocatalysts and contacting it with theolefin(s). Alternatively, the support may first be contacted (reacted)with a cocatalyst (if needed) such as an alkylaluminum compound, andthen contacted with an appropriate Ni compound. The support may also beable to take the place of a Lewis or Bronsted acid, for instance, anacidic clay such as montmorillonite, if needed. Another method of makinga supported catalyst is to start a polymerization or at least make anickel complex of another olefin or oligomer of an olefin such ascyclopentene on a support such as silica or alumina. These“heterogeneous” catalysts may be used to catalyze polymerization in thegas phase or the liquid phase. By gas phase is meant that a gaseousolefin is transported to contact with the catalyst particle.

[0098] In all of the polymerization processes described herein oligomersand polymers of the various olefins are made. They may range inmolecular weight from oligomeric olefins, to lower molecular weight oilsand waxes, to higher molecular weight polyolefins. One preferred productis a polymer with a degree of polymerization (DP) of about 10 or more,preferably about 40 or more. By “DP” is meant the average number ofrepeat (monomer) units in a polymer molecule.

[0099] Depending on their properties, the polymers made by the processesdescribed herein are useful in many ways. For instance if they arethermoplastics, they may be used as molding resins, for extrusion,films, etc. If they are elastomeric, they may be used as elastomers. Ifthey contain functionalized monomers such as acrylate esters, they areuseful for other purposes, see for instance previously incorporated U.S.Pat. No. 5,880,241.

[0100] Depending on the process conditions used and the polymerizationcatalyst system chosen, polymers, even those made from the samemonomer(s) may have varying properties. Some of the properties which maychange are molecular weight and molecular weight distribution,crystallinity, melting point, and glass transition temperature. Exceptfor molecular weight and molecular weight distribution, branching canaffect all the other properties mentioned, and branching may be varied(using the same nickel compound) using methods described in previouslyincorporated U.S. Pat. No. 5,880,241.

[0101] It is known that blends of distinct polymers, that-vary forinstance in the properties listed above, may have advantageousproperties compared to “single” polymers. For instance it is known thatpolymers with broad or bimodal molecular weight distributions may bemelt processed (be shaped) more easily than narrower molecular weightdistribution polymers. Thermoplastics such as crystalline polymers mayoften be toughened by blending with elastomeric polymers.

[0102] Therefore, methods of producing polymers which inherently producepolymer blends are useful especially if a later separate (and expensive)polymer mixing step can be avoided. However in such polymerizations oneshould be aware that two different catalysts may interfere with oneanother, or interact in such a way as to give a single polymer.

[0103] In such a process the Ni containing polymerization catalystdisclosed herein can be termed the first active polymerization catalyst.Monomers useful with these catalysts are those described (and alsopreferred) above. A second active polymerization catalyst (andoptionally one or more others) is used in conjunction with the firstactive polymerization catalyst. The second active polymerizationcatalyst may be another late transition metal catalyst, for example asdescribed in previously incorporated W098/30609, U.S. Pat. Nos.5,880,241 and 6,060,569, as well as in 5,714,556 and 5,955,555, whichare also incorporated by reference herein for all purposes as if fullyset forth.

[0104] Other useful types of catalysts may also be used for the secondactive polymerization catalyst. For instance so-called Ziegler-Nattaand/or metallocene-type catalysts may also be used. These types ofcatalysts are well known in the polyolefin field, see for instanceAngew. Chem., Int. Ed. Engl., vol. 34, p. 1143-1170 (1995), EP-A-0416815and U.S. Pat. No. 5,198,401 for information about metallocene-typecatalysts, and J. Boor Jr., Ziegler-Natta Catalysts and Polymerizations,Academic Press, New York, 1979 for information about Ziegler-Natta-typecatalysts, all of which are incorporated by reference herein for allpurposes as if fully set forth. Many of the useful polymerizationconditions for all of these types of catalysts and the first activepolymerization catalysts coincide, so conditions for the polymerizationswith first and second active polymerization catalysts are easilyaccessible. Oftentimes the “co-catalyst” or “activator” is needed formetallocene or Ziegler-Natta-type polymerizations. In many instances thesame compound, such as an alkylaluminum compound, may be used as an“activator” for some or all of these various polymerization catalysts.

[0105] In one preferred process described herein the first olefin(s)(the monomer(s) polymerized by the first active polymerization catalyst)and second olefin(s) (the monomer(s) polymerized by the second activepolymerization catalyst) are identical, and preferred olefins in such aprocess are the same as described immediately above. The first and/orsecond olefins may also be a single olefin or a mixture of olefins tomake a copolymer. Again it is preferred that they be identicalparticularly in a process in which polymerization by the first andsecond active polymerization catalysts make polymer simultaneously.

[0106] In some processes herein the first active polymerization catalystmay polymerize a monomer that may not be polymerized by said secondactive polymerization catalyst, and/or vice versa. In that instance twochemically distinct polymers may be produced. In another scenario twomonomers would be present, with one polymerization catalyst producing acopolymer, and the other polymerization catalyst producing ahomopolymer, or two copolymers may be produced which vary in the molar;proportion or repeat units from the various monomers. Other analogouscombinations will be evident to the artisan.

[0107] In another variation of this process one of the polymerizationcatalysts makes an oligomer of an olefin, preferably ethylene, whicholigomer has the formula R⁷⁰ CH═CH₂, wherein R⁷⁰ is n-alkyl, preferablywith an even number of carbon atoms. The other polymerization catalystin the process them (co)polymerizes this olefin, either by itself orpreferably with at least one other olefin, preferably ethylene, to forma branched polyolefin. Preparation of the oligomer (which is sometimescalled an (-olefin) by a second active polymerization-type of catalystcan be found in previously incorporated U.S. Pat. Nos. 5,880,241 as wellas 6,103,946 (also incorporated by reference for all purposes as iffully set forth).

[0108] Likewise, conditions for such polymerizations, using catalysts ofthe second active polymerization type, will also be found in theappropriate above mentioned references.

[0109] Two chemically different active polymerization catalysts are usedin this polymerization process. The first active polymerization catalystis described in detail above. The second active polymerization catalystmay also meet the limitations of the first active polymerizationcatalyst, but must be chemically distinct. For instance, it may have adifferent transition metal present, and/or utilize a different type ofligand and/or the same type of ligand which differs in structure betweenthe first and second active polymerization catalysts. In one preferredprocess, the ligand type and the metal are the same, but the ligandsdiffer in their substituents.

[0110] Included within the definition of two active polymerizationcatalysts are systems in which a single polymerization catalyst is addedtogether with another ligand, preferably the same type of ligand, whichcan displace the original ligand coordinated to the metal of theoriginal active polymerization catalyst, to produce in situ twodifferent polymerization catalysts.

[0111] The molar ratio of the first active polymerization catalyst tothe second active polymerization catalyst used will depend on the ratioof polymer from each catalyst desired, and the relative rate ofpolymerization of each catalyst under the process conditions. Forinstance, if one wanted to prepare a “toughened” thermoplasticpolyethylene that contained 80% crystalline polyethylene and 20% rubberypolyethylene, and the rates of polymerization of the two catalysts wereequal, then one would use a 4:1 molar ratio of the catalyst that gavecrystalline polyethylene to the catalyst that gave rubbery polyethylene.More than two active polymerization catalysts may also be used if thedesired product is to contain more than two different types of polymer.

[0112] The polymers made by the first active polymerization catalyst andthe second active polymerization catalyst may be made in sequence, i.e.,a polymerization with one (either first or second) of the catalystsfollowed by a polymerization with the other catalyst, as by using twopolymerization vessels in series. However it is preferred to carry outthe polymerization using the first and second active polymerizationcatalysts in the same vessel(s), i.e., simultaneously. This is possiblebecause in most instances the first and second active polymerizationcatalysts are compatible with each other, and they produce theirdistinctive polymers in the other catalyst's presence. Any of theprocesses applicable to the individual catalysts may be used in thispolymerization process with 2 or more catalysts, i.e., gas phase, liquidphase, continuous, etc.

[0113] Catalyst components which include Ni complexes of (I), with orwithout other materials such as one or more cocatalysts and/or otherpolymerization catalysts are also disclosed herein. For example, such acatalyst component could include the Ni complex supported on a supportsuch as alumina, silica, a polymer, magnesium chloride, sodium chloride,etc., with or without other components being present. It may simply be asolution of the Ni complex, or a slurry of the Ni complex in a liquid,with or without a support being present.

[0114] The polymers produced by this process may vary in molecularweight and/or molecular weight distribution and/or melting point and/orlevel of crystallinity, and/or glass transition temperature and/or otherfactors. For copolymers the polymers may differ in ratios of comonomersif the different polymerization catalysts polymerize the monomerspresent at different relative rates. The polymers produced are useful asmolding and extrusion resins and in films as for packaging. They mayhave advantages such as improved melt processing, toughness and improvedlow temperature properties.

[0115] Hydrogen or other chain transfer agents such as silanes (forexample trimethylsilane or triethylsilane) may be used to lower themolecular weight of polyolefin produced in the polymerization processherein. It is preferred that the amount of hydrogen present be about0.01 to about 50 mole percent of the olefin present, preferably about 1to about 20 mole percent. When liquid monomers (olefins) are present,one may need to experiment briefly to find the relative amounts ofliquid monomers and hydrogen (as a gas). If both the hydrogen andmonomer(s) are gaseous, their relative concentrations may be regulatedby their partial pressures.

[0116] In the Examples, all pressures are gauge pressures. Branching wasdetermined by ¹H NMR, taking the total of the methyl carbon atoms as thenumber of branches. Branching is uncorrected for end groups. Thefollowing abbreviations are used:

[0117] BINAP—see compound (XI)

[0118] dba—dibenzylideneacetone

[0119] EtOAc—ethyl acetate

[0120] EtOH—ethanol

[0121] Mn—number average molecular weight

[0122] Mp—melting point

[0123] NEt₃—triethylamine

[0124] PDI—weight average molecular weight/number average molecularweight

[0125] PhCl—chlorobenzene

[0126] RT—room temperature

[0127] THF—tetrahydrofuran

[0128] Tm—melting point

EXAMPLES 1-11 Preparation of 2-Anilinotropones General Procedure A—TheConversion of 2-Triflatotropone to 2-Anilinotropones with LiquidAnilines

[0129] A Schlenk tube, flame-dried in vacuo, was placed under an Aratmosphere on a vacuum line. The tube was charged with Pd₂(dba)₃ (5 mg,0.005 mmol), rac-BINAP (7 mg, 0.01 mmol), Cs₂CO₃ (456 mg, 1.4 mmol), and2-triflatotropone (254 mg, 1.0 mmol). Toluene (2 mL) was added followedby the appropriate aniline (1.2 mmol). The Schlenk tube was sealed andheated to 80° C. for approximately 12 h. The reaction mixture wasallowed to cool to RT, filtered through a pad of silica gel with the aidof ethyl ether (100 mL), and concentrated to afford the crude product.Purification was effected via flash column chromatography on silica gel.

General Procedure B—The Conversion of 2-Triflatotropone to2-Anilinotropones with Solid Anilines

[0130] A Schlenk tube, flame-dried in vacuo, was placed under an Aratmosphere on a vacuum line. The tube was charged with Pd₂(dba)₃ (5 mg,0.005 mmol), rac-BINAP (7 mg, 0.01 mmol), Cs₂CO₃ (456 mg, 1.4 mmol),2-triflatotropone (254 mg, 1.0 mmol), and the appropriate aniline (1.2mmol). Toluene (2 mL) was added and the Schlenk tube was sealed andheated to 80° C. for approximately 12 h. The reaction mixture wasallowed to cool to RT, filtered through a pad of silica gel with the aidof ethyl ether (100 mL), and concentrated to afford the crude product.Purification was effected via flash column chromatography on silica gel.

[0131] The individual Examples 1-11 below give the aniline used toproduce the corresponding 2-anilinotropone (substitution patter on thephenyl rings remained the same).

EXAMPLE 1

[0132] General procedure A was used to convert 2,6-dimethylaniline (148μl, 1.2 mmol) to the desired product in 15 h. Purification via flashcolumn chromatography (eluants 3:2 hexane:ether) afforded 201 mg (90%yield) of an orange solid. Mp: 76-78° C. ¹H NMR (250 MHz, CDCl₃): δ8.40(bs, 1 H); 7.32 (m, 2 H); 7.18 (m, 3 H); 7.08 (t, J=10.5 Hz, 1 H); 6.73(m, 1 H); 6.22 (d, J=10.5 Hz, 1 H); 2.15 (s, 6 H). ¹³C NMR (100 MHz,CDCl₃) : δ176.6, 154.6, 137.3, 136.3, 136.2, 135.1, 129.9, 128.7, 127.8,123.5, 109.6, 18.0. Anal. Calcd for C₁₅H₁₅NO: C, 79.97; H, 6.71; N,6.22. Found: C, 79.92; H, 6.71; N, 6.05.

EXAMPLE 2

[0133] General procedure A was used to convert 2,6-di-i-propylaniline(227 μl, 1.2 mmol) to the desired product in 14 h. Purification viaflash column chromatography (eluants 2:1 hexane:ether) afforded 242 mg(86% yield) of an orange solid. Mp: 86-88° C. ¹H NMR (200 MHz,CDC1₃):δ8.42 (bs, 1 H); 7.43-7.24 (m, 5 H); 7.06 (t, J=10.2 Hz,l H);6.71 (m, 1 H); 6.26 (d, J=10.2 Hz, 1 H); 2.90 (m, 2 H); 1.15 (d, J=7.0Hz, 6 H); 1.11 (d, J=7.0 Hz, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ176.5,156.4, 146.9, 137.5, 136.2, 132.5, 130.0, 128.9, 124.4, 123.6, 110.4,28.6, 24.6, 23.4. Anal. Calcd for C₁₉H₂₃NO: C, 81.10; H, 8.24; N, 4.98.Found: C, 81.15; H, 8.20; N, 4.94.

EXAMPLE 3

[0134] General procedure A was used to convert 2-tbutylaniline (187 μl,1.2 mmol) to the desired product in 16 h. Purification via flash columnchromatography (eluants 3:1 hexane:ether) afforded 221 mg (88% yield) ofan orange solid. Mp: 92-940C. ¹H NMR (250 MHz, CDCl₃):δ8.80 (bs, 1 H);7.53 (m, 1 H); 7.35-7.25 (m, 4 H); 7.20 (m, 1 H); 7.10 (d, J=10.2 Hz, 1H); 6.75 (m, 2 H); 1.37 (3, 9 H). ¹³C NMR (100 MHz, CDCl₁₃):δ176.8,155.2, 146.8, 137.5, 136.8, 136.2, 130.0, 128.6, 127.7, 127.3, 127.2,123.7, 110.8, 35.1, 30.5. Anal. Calcd for C₁₇H₁₉gNO: C, 80.59; H, 7.56;N, 5.53. Found: C, 80.34; H, 7.52; N, 5.51.

EXAMPLE 4

[0135] General procedure A was used to convert 2-t-butyl-6-methylaniline(196 mg, 1.2 mmol) to the desired product in 15.5 h. Purification viaflash column chromatography (eluants 2:1 hexane:ether) afforded 97 mg(36% yield) of an orange solid. Mp: 115-117° C. ¹H NMR (200 MHz, CDC1₃): δ8.69 (bs, 1 H); 7.41-7.18 (m, 5 H); 7.09 (t, J=10.2 Hz, 1 H); 6.73(m, 1 H); 6.17 (d, J=10.2 Hz, 1 H); 2.06 (s, 3 H); 1.32 (s, 9 H). ²³CNMR (100 MHz, CDCl₃): δ176.7, 155.2, 148.4, 137.6, 135.1, 130.0, 129.5,127.9, 125.4, 123.6, 111.0, 35.5, 31.1, 18.6. Anal. Calcd for C,₁₈H₂₁NO:C, 80.86; H, 7.92; N, 5.24. Found: C, 80.61; H, 7.93; N, 5.14.

EXAMPLE 5

[0136] General procedure B was used to convert 2,6-dichloroaniline (194mg, 1.2 mmol) to the desired product in 14.5 h. Purification via flashcolumn chromatography (eluants 2:1 hexane:ether) afforded 200 mg (75%yield) of an orange solid. Mp: 63-65° C. 1H NMR (200 MHz, CDCl₁₂) :δ8.48 (bs, 1 H); 7.47 (d, J=8.0 Hz, 2 H); 7.37 (m, 2 H); 7.26 (t, J=8.0Hz, 1 H); 7.13 (t, J=10.2 Hz, 1 H); 6.83 (m, 1 H); 6.29 (d, J=10.2 Hz, 1H). ¹³C NMR (100 MHz, CDCl₃):δ177.1, 152.4, 137.5, 135.7, 134.0, 133.5,131.7, 129.0, 128.7, 125.3, 111.3. Anal. Calcd for C₁₃H₉NOCl₂: C, 58.67;H, 3.41; N, 5.26. Found: C, 58.78; H, 3.46; N, 5.22.

EXAMPLE 6

[0137] General procedure B on half the scale with the modification of 12mg (0.0125 mmol) Pd₂dba₃ and 16 mg (0.025 mmol) rac-BINAP was used toconvert 2,6-dibromoaniline (151 mg, 0.60 mmol) to the desired product in15 h. Purification via flash column chromatography (eluants 2:1hexane:ether) afforded 122 mg (69% yield) of an orange solid. Mp: 73-75°C. Hz, 2 H); 7.35 (m,2 H); 7.12 (m, 2 H); 6.83 (m, 1 H); 6.27 (d, J=10.2Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃) : δ177.1, 152.5, 137.6, 136.3, 135.4,133.0, 131.9, 129.9, 125.3, 124.4, 111.3. Anal. Calcd for C₁₃H₉NOBr₂: C,43.98; H, 2.56; N, 3.95. Found: C, 43.88; H, 2.61; N, 3.88.

EXAMPLE 7

[0138] General procedure B was used to convert2,3,4,5,6-pentafluoroaniline (220 mg, 1.2 mmol) to the desired productin 15.5 h. Purification via flash column chromatography (eluants 2:1hexane:ether) afforded 256 mg (84% yield) of a green solid. The compoundwas isolated as a hydrate. Mp: 156-158° C. ¹H NMR (400 MHz, CDCl₃):δ8.19 (bs, 1 H); 7.38 (dd, J=8.2, 11.8 Hz, 1 H); 7.32 (d, J=11.0 Hz, 1H); 7.15 (t, J=10.2 Hz, 1 H) ; 6.87 (t, J=9.0 Hz, 1 H); 6.49 (dt, J=2.6,10.0 Hz, 1 H); 2.14 (s, 2 H, coordinated H₂O). ¹³C NMR (100 MHz, CDCl₃): δ177.2, 151.6, 143.0 (dm, J=250 Hz), 139.7 (dm, J=253 Hz), 138.1 (dm,J=253 Hz), 137.7, 135.2, 132.5, 126.4, 113.7 (dt, J=3.8, 14.2 Hz),111.6. ¹⁹F NMR (376 MHz, CDCl₁₃) : δ−144.5 (m), −157.31 (m), −161.87(m). Anal. Calcd for C₁₃H₆NOF₅: C, 54.36; H, 2.11; N, 4.88. Found: C,54.31; H, 2.18; N, 4.81.

EXAMPLE 8

[0139] General procedure A was used to convert3,5-bistrifluoromethylaniline (188 μl, 1.2 mmol) to the desired productin 15.5 h. Purification via flash column chromatography (eluants 2:1hexane:ether) afforded 313 mg (89% yield) of a green solid. Compound wasisolated as a hydrate. ¹H NMR (400 MHz, CDCl₃): δ8.87 (bs, 1 H) ; 7.75(s, 2 H); 7.66 (s, 1 H); 7.38 (dd, J=8.5, 11.8 Hz, 1 H); 7.31 (d, J=11.8Hz, 1 H); 7.20 (m, 2 H); 6.89 (m, 1 H); 2.15 (s, 2.7 H, coordinatedH₂O). ¹³C NMR (100 MHz, CDCl₁₃) : δ117.5, 151.7, 140.8, 137.8, 135.4,132.9 (q, J=33.5 Hz), 132.3, 126.6, 122.9 (q, J=271 Hz), 122.7, (d,J=2.9 Hz), 117.9 (t, J=3.4 Hz), 111.1. ¹⁹F NMR (376 MHz, CDCl₃): δ−63.6(s)

EXAMPLE 9

[0140] General procedure B was used to convert 2,6-diphenylaniline (294mg, 1.2 mmol) to the desired product in 16.5 h. Purification via flashcolumn chromatography (eluants 2:1 hexane:ether) afforded 127 mg (37%yield) of a yellow solid.

EXAMPLE 10

[0141] General procedure A was used to convert 2,6-difluoroaniline (129μl, 1.2 mmol) to the desired product in 19 hours. Purification via flashcolumn chromatography (eluants 2:1 hexane:ether) afforded 219 mg (94%yield) of a yellow solid. ¹ H NMR (400 MHz, CDCl₃) : δ8.30 (bs, 1 H);7.35 (m, 2 H); 7.25 (m, 1 H); 7.16 (t, J=10.2 Hz, 1 H); 7.05 (m, 2 H);6.84 (m, 1 H); 6.55 (dt, J=2.5, 10.2 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ177.0, 159.0 (d, J=4.6 Hz), 156.5 (d, J=4.6 Hz), 137.3, 135.5, 131.6,127.3 (t, J=9.6 Hz), 125.2, 115.5 (t, J=15.6 Hz), 112.1 (m), 111.4. ¹⁹FNMR (376 MHz, CDCl₃) : δ−116.6 (s). Anal. Calcd for C₁₃H₉NOF₂: C, 66.93;H, 3.89; N, 6.01. Found: C, 66.66; H, 3.90; N, 5.97.

EXAMPLE 11

[0142] General procedure A was used to convert2-methyl-6-trifluoromethylaniline (630 μl, 3.6 mmol) to the desiredproduct in 14.5 hours. Purification via flash column chromatography(eluants 2:1 hexane:ether) afforded 781 mg (93% yield). ¹H NMR (400 MHz,CDCl₃) : δ8.50 (bs, 1 H); 7.64 (d, J =7.8 Hz, 1 H); 7.55 (d, J=7.6 Hz, 1H); 7.41 (at, J=7.8 Hz, 1 H); 7.33 (m, 2 H); 7.07 (at, J=10.2 Hz, 1 H);6.77 (m, 1 H); 6.14 (d, J=10.1 Hz, 1 H); 2.17 (s, 3 H). ¹³C NMR (100MHz, CDC1₃): δ176.8, 154.2, 138.6, 137.4, 135.8, 134.9, 134.5, 131.1,128.4 (q, J=29.6 Hz), 127.6, 124.8 (q, J=5.2 Hz), 124.4, 123.3 (q, J=272Hz), 110.5, 17.7. ³¹p NMR (377 MHz, C₆D₆): δ−62.2. Anal. Calcd forC₁₅H₁₂NOF₃: C, 64.51; H, 4.33; N, 5.02. Found: C, 64.23; H, 4.24; N,4.87.

EXAMPLE 12

[0143] General procedure A was used to convert 2-methylaniline (384 μL,3.6 mmol) to the desired product in 14.5 hours. Purification via flashcolumn chromatography (eluants 2:1 hexane:ether) afforded 561 mg (89%yield). ¹H NMR (400 MHz, CDCl₃) : δ8.57 (bs, 1 H) ; 7.40-7.30 (m, 3 H) ;7.30-7.21 (m, 3 H); 7.12 (dd, J=10, 10.4 Hz, 1 H); 6.77 (m, 1 H); 6.71(d, J=10.4 Hz, 1 H) ; 2.21 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): 6 176.5,154.5, 137.5, 136.5, 136.2, 134.6, 131.4, 130.2, 127.1, 126.1, 124.2,110.6, 17.8. Anal. Calcd for C₁₄H₁₃NO: C, 79.59; H, 6.20; N, 6.63.Found: C, 79.62; H, 6.17; N, 6.62.

EXAMPLES 13-22

[0144] General Procedure for the Synthesis of Na Salts of2-Anilinotropones: To a side arm flask in a glovebox was added NaH (1.2equiv). The flask was removed from the glovebox and placed on a vacuumline under argon. THF (5-10 mL) was added to the flask, and the flaskwas cooled with an ice water bath. Slow addition of the 2-anilinotropone(1 equiv) as a solution in THF (3 mL) resulted in vigorous bubbling.When bubbling ceased, the flask was removed from the ice water bath andallowed to warm to rt. After 2 h, the solution was cannula filtered awayfrom the remaining NaH, and the residual NaH was washed with THF (3 mL).The THF was removed in vacuo to produce essentially a quantitative yieldof the desired salt as its THF adduct. The amount of THF incorporatedvaried with different salts and was determined by ¹H NMR.

EXAMPLE 13

[0145] Na Salt of 2-(2,6-diisopropylanilino)tropone: The generalprocedure was employed with 1.28 g (4.5 mmol) anilinotropone and 120 mg(5 mmol) NaH. The salt was isolated with 1 equiv of THF. ¹H NMR (250MHz, C6D₆): δ7.18-7.04 (m, 3 H); 6.6-6.4 (m, 3 H); 6.32 (dd, J=8.0, 12.2Hz, 1 H); 6.02 (dt, J=3.2, 7.8 Hz, 1 H); 3.36 (THF); 2.94 (m, 2 H); 1.26(THF); 1.14 (d, j =7.0 Hz, 6 H); 1.00 (d, J=7 Hz, 1 H). ¹³C NMR (100MHz, C₆D₆) : δ177.6, 165.8, 148.7, 139.0, 134.4, 133.5, 124.2, 123.5,121.2, 118.4, 117.9, 68.0, 28.2, 25.6, 24.9, 23.9.

EXAMPLE 14

[0146] Na Salt of 2-(2,6-dimethylanilino)tropone: The general procedurewas employed with 405 mg (1.8 mmol) anilinotropone and 50 mg (2 mmol)NaH. The salt was isolated with 2.18 equiv of THF. ¹H NMR (400 MHz,C₆D₆): δ7.05 (m, 2 H) ; 6.92 (m, 1 H); 6.58-6.33 (m, 4 H); 6.05 (m, 1H); 3.40 (THF); 1.94 (s, 6 H) ; 1.31 (THF).

EXAMPLE 15

[0147] Na Salt of 2-(2-t-butylanilino)tropone: The general procedure wasemployed with 462 mg (1.8 mmol) anilinotropone and 50 mg (5 mmol) NaH.The salt was isolated with 1.5 equiv of THF. ¹H NMR (250 MHz, C₆D₆) :δ7.42 (d, J=8.0 Hz, 1 H); 6.98 (m, 1 H); 6.66 (m, 2 H); 6.45 (m, 3 H);6.04 (at, J=9.0 Hz, 1 H); 3.44 (THF); 1.37 (THF); 1.29 (s, 9 H).

EXAMPLE 16

[0148] Na Salt of 2-(2-t-butyl-6-methylanilino)tropone: The generalprocedure was employed with 303 mg (1.14 mmol) anilinotropone and 31 mg(1.3 mmol) NaH. The salt was isolated with 1.16 equiv of THF. 1H NMR(400 MHz, C₆D₆) : δ7.33 (d, J =7.6 Hz, 1 H); 7.07 (d, J=7.6 Hz, 1 H);6.94 (at, J=7.6 Hz, 1 H); 6.52 (m, 2 H); 6.39 (m, 2 H); 6.04 (m, 1 H);3.40 (THF); 1.97 (s, 3 H); 1.30 (s, 9 H+THF).

EXAMPLE 17

[0149] Na Salt of 2-(2,6-diphenylanilino)tropone: The general procedurewas employed with 352 mg (1.0 mmol) anilinotropone and 28 mg (1.2 mmol)NaH. The salt was isolated with 0.55 equiv of THF. 1H NMR (400 MHz,C₆D₆) : δ7.28 (d, J=7.6 Hz, 2 H); 7.19 (d, J=6.8 Hz, 2 H); 7.04 (t,J=7.6 Hz, 1 H); 6.81 (m, 6 H); 6.63 (d, J=11.6 Hz, 1 H); 6.44 (m, 2 H) ;6.08 (at, J=9.0 Hz, 1 H) ; 6.00 (d, J=10.4 Hz, 1 H) 3.52 (THF); 1.39(THF).

EXAMPLE 18

[0150] Na Salt of 2-(2-methyl-6-trifluoromethylanilino)-tropone: Thegeneral procedure was employed with 688 mg (2.5 mmol) anilinotropone and71 mg (2.95 mmol) NaH. The salt was isolated with 1 equiv of THF. ¹H NMR(400 MHz, C₆D₆) : δ7.39 (d, J=7.6 Hz, 1 H); 7.06 (d, J=7.6 Hz, 1 H);6.70 (at, J=7.6 Hz, 1 H); 6.57 (m, 2 H); 6.45 (dd, J=8.2, 11.6 Hz, 1 H);6.28 (d, J=11.6 Hz, 1 H); 6.08 (at, J=8.8 Hz, 1 H); 3.46 (THF); 1.88(s,3 H); 1.33(THF).

EXAMPLE 19

[0151] Na Salt of 2-(2,6-dichloroanilino)tropone: The general procedurewas employed with 658 mg (2.5 mmol) anilinotropone and 71 mg (2.95 mmol)NaH. The salt was isolated with 1.6 equiv of THF. ¹H NMR (400 MHz, C₆D₆): δ7.08 (d, J=8.0 Hz, 2 H); 6.73 (d, J=10.4 Hz, 1 H); 6.59 (at, J=10.2Hz, 1 H); 6.51 (m, 1 H); 6.39 (m, 2 H); 6.11 (at, J=9.2 Hz, 1 H) ; 3.50(THF) ; 1.35 (THF).

EXAMPLE 20

[0152] Na Salt of 2-(2,6-dibromoanilino)tropone: The general procedurewas employed with 721 mg (2.0 mmol) anilinotropone and 58 mg (2.44 mmol)NaH. The salt was isolated with 1 equiv of THF. 1H NMR (400 MHz, C₆D₆) :δ7.26 (m, 2 H) ; 6.74 (m, 1 H); 6.61 (m, 1 H); 6.50 (m, 1 H); 6.35 (d,J=11.2 Hz, 1 H); 6.23 (m, 1 H); 6.14 (m, 1 H); 3.51 (THF); 1.33 (THF).

EXAMPLE 21

[0153] Na Salt of 2-(2-methylanilino)tropone: The general procedure wasemployed with 508 mg (2.4 mmol) anilinotropone and 69 mg (2.9 mmol) NaH.The salt was isolated with 0.89 equiv of THF. ¹H NMR (400 MHz, C₆D₆) :δ7.11 (m, 2 H); 6.93 (m, 1 H); 6.64-6.45 (m, 4 H); 6.41 (dd, J=8.6, 11.4Hz, 1 H); 6.08 (at, J=9.0 Hz, 1 H); 3.46 (THF); 1.89 (s, 3 H); 1.32(THF).

Example 22

[0154] Na Salt of 2-(2,3,4,5,6-pentafluoroanilino)tropone: The generalprocedure was employed with 581 mg (1.9 mmol) anilinotropone and 100 mg(4.2 mmol) NaH. The salt was isolated with no excess THF. ¹H NMR (400MHz, d₆-acetone): δ6.85 (at, H=10.2 Hz, 1 H); 6.73 (d, J=10 Hz, 1 H);6.69 (at J=11.4 Hz, 1 H); 6.19 (d, J=11.2 Hz, 1 H); 6.14 (at, J=9.2 Hz,1 H).

EXAMPLES 23-32

[0155] General Procedure for the Synthesis of Ni Complexes: To a flamedried Schlenk flask in a glovebox were added the sodium salt of a2-anilinotroponeeTHF (1 equiv) and (Ph₃P) ₂Ni (Ph) (Cl) (1 equiv). Theflask was removed from the glovebox, was placed on a vacuum line underAr, and was cooled to −30° C. with a dry ice/acetone bath. THF (˜15 mL)was added to the flask, which was allowed to warm to RT over 1 h. Thereaction was allowed to stir at ambient temperature for 1 h. THF wasremoved in vacuo and the crude reaction mixture dissolved in toluene(˜15 mL). Cannula transfer onto a pad of Celite was followed byfiltration under Ar. The Celite® pad was washed with toluene (3×5 mL),and the solvent volume was reduced to 3-5 mL. Pentane (50 mL) was added,and the Schlenk flask was placed in a −30° C. freezer overnight. Solventwas removed from the precipitate via cannula filtration, and theresidual solid was washed with pentane (3×10 mL). Drying in vacuoproduces the desired nickel complex.

EXAMPLE 23

[0156]2-(2,6-Diisopropylanilino)tropone Ni Complex (VIII): The generalprocedure was employed with 201 mg (0.54 mmol) of the sodium salt and372 mg (0.54 mmol) of (Ph₃P)₂Ni(Ph) (Cl) to afford 241 mg (67%) of thedesired complex as a yellow-orange solid. ¹H NMR (400 MHz, C₆D₆): δ7.63(m, 6 H); 7.08 (d, J=7.0 Hz, 2 H); 6.98 (m, 12 H); 6.76 (d, J=10.4 Hz, 1H); 6.58 (at, J=9.9 Hz, 1 H). 6.53 (d, J=11.5 Hz, 1 H); 6.45-6.33 (m, 4H); 6.13 (at, J=9.4 Hz, 1 H); 3.82 (sept, J=6.8 Hz, 2 H); 1.32 (d, J=6.8Hz, 6 H); 1.09 (d, J=6.8 Hz, 6 H). ¹³C NMR (100 MHz, C₆D₆): δ180.2 (d,J=7.6 Hz), 169.6 148.9 (d, J=45 Hz), 144.4, 142.3, 138.1 (d, J=2.2 Hz),134.6 (d, J=10.5 Hz), 133.1, 132.0, 131.6, 129.9 (d, J=1.9 Hz), 125.9,125.5 (d, J=2 Hz), 123.7, 122.2, 121.7, 121.3, 121.1, 29.0, 25.9, 23.9.31p NMR (162 MHz, C₆D₆) : δ28.9. Anal. Calcd for C₄₃H₄₂NOPNi: C, 76.12;H, 6.24; N, 2.06. Found: C, 75.83; H, 6.24; N, 1.98.

EXAMPLE 24

[0157]2-(2,6-dimethylanilino)tropone Ni Complex: The general procedurewas employed with 172 mg (0.54 mmol) of the sodium salt and 372 mg (0.54mmol) of (Ph₃P)₂Ni(Ph) (Cl) to afford 190 mg (57%) of the desiredcomplex as a yellow-orange solid. ¹H NMR (400 MHz, CD₂Cl₂): δ7.54 (m, 6H); 7.39 (m, 3 H); 7.28 (m, 6 H); 7.21 (d, J=8 Hz, 2 H); 7.09 (dd, J=10,10.6 Hz, 1 H); 6.99 (m, 2 H); 6.94 (d, J=10.6 Hz, 1 H); 6.71 (d, J=10.7Hz, 1 H); 6.63 (at, J=9.5 Hz, 1 H); 6.56 (t, J=8 Hz, 1 H); 6.22 (m, 2H); 6.14 (m, 2 H); 2.21 (s, 6 H). ¹³C NMR (100 MHz, CD₂Cl₂) : δ179.9 (d,J=7.2 Hz), 167.7, 150.3 (d, J=44.5 Hz), 146.4, 136.9 (d, J=1.8 Hz),134.7, 134.6 (d, J=10.7 Hz), 134.3, 131.8 (d, J=1.9 Hz), 131.4, 130.1,128.2 (d, J=9.7 Hz), 127.7, 124.8 (d, J=2.6 Hz), 124.3, 122.0, 121.1,120.5, 117.7, 18.3. ³¹p NMR (162 MHz, C₆D₆): δ29.03. Anal. Calcd forC₃₉H₃₄NOPNi: C, 75.26; H, 5.51; N, 2.25. Found: C, 75.49; H, 5.57; N,2.38.

EXAMPLE 25

[0158]2-(2-t-Butylanilino)tropone Ni Complex: The general procedure wasemployed with 201 mg (0.53 mmol) of the sodium salt and 372 mg (0.54mmol) of (Ph₃P)₂Ni(Ph) (Cl) to afford 195 mg (57%) of the desiredcomplex as a yellow-orange solid. ¹H NMR (400 MHz, CD₂Cl₂): δ7.47 (m, 6H); 7.38 (m, 3 H); 7.28 (m, 6 H); 7.18 (dd, J=1.4, 8 Hz, 1 H); 7.11 (bs,1 H); 6.95 (at, J=10.2 Hz, 1 H); 6.81 (m, 2 H); 6.72 (m, 1 H); 6.55 (M,2 H); 6.46 (d, J=9.4 Hz, 1 H); 6.42 (dd, J=1.6, 7.7 Hz, 1 H); 6.23 (m, 2H); 6.07 (bs, 1 H); 1.51 (s, 9 H). ¹³C NMR (100 MHz, CD₂Cl₂) : δ179.9(d, J=7.5 Hz), 169.1, 151.3 (d J=45 Hz), 146.9, 142.3, 138.4 (broad),137.8 (broad), 134.8, 134.6 (d, J=10.5 Hz), 133.7, 131.9, 131.5, 130.1(d, J=1.9 Hz), 128.9, 128.8, 128.2 (d, J=9.7 Hz), 126.3, 125.1 (broad),124.2, 121.6, 120.9, 120.7, 120.5, 36.4, 32.8. ³¹p NMR (162 MHz,CD₂Cl₂): δ29.34. Anal. Calcd for C₄₁H₃₈NOPNi: C, 75.71; H, 5.89; N,2.15. Found: C, 75.76; H, 5.92; N, 2.19.

Example 26

[0159]2-(2-t-Butyl-6-methylanilino)tropone Ni Complex: The generalprocedure was employed with 219 mg (0.59 mmol) of the sodium salt and409 mg (0.59 mmol) of (Ph₃P)₂Ni(Ph) (Cl) to afford 185 mg (47%) of thedesired complex as a yellow-orange solid. ¹H NMR (400 MHz, C₆D₆): δ7.63(m, 6 H); 7.23 (bs, 1 H); 7.15 (m, 1 H); 6.98 (m, 10 H); 6.81 (m, 2 H);6.75 (d, J=10.4 Hz, 1 H); 6.58 (at, J=10 Hz, 1 H); 6.48 (m, 2 H); 6.41(m, 3 H); 6.11 (at, J=9.0 Hz, 1 H); 2.46 (s, 3 H); 1.69 (s, 9 H). ¹³CNMR (100 MHz, CD₂C₂) : δ179.8 (d, J=7.3 Hz), 168.1, 149.3 (d, J=45.3Hz), 145.6, 142.1, 138.3 (broad), 137.2 (broad), 134.7, 134.5 (d, J=10.5Hz), 133.9, 133.1, 131.9, 131.4, 130.1, 128.2 (d, J=9.9 Hz), 128.1,127.1, 124.9 (broad), 124.4, 121.7, 121.1, 120.4, 119.7, 36.9, 33.3,19.6. ³¹P NMR (162 MHz, CD₂C1₂): δ29.02. Anal. Calcd for C₄₂H₄₀NOPNi: C,75.92; H, 6.07; N, 2.11. Found: C, 75.75; H, 6.11; N, 2.15.

EXAMPLE 27

[0160]2-(2,6-Diphenylanilino)tropone Ni Complex: The general procedurewas employed with 225 mg (0.55 mmol) of the sodium salt and 380 mg (0.55mmol) of (Ph₃P)₂Ni(Ph) (Cl) to afford 220 mg (54%) of the desiredcomplex as a yellow-orange solid. Compound was isolated with 0.33 eq oftoluene. ¹H NMR (400 MHz, C₆D₆): δ7.95 (d, J=7.6 Hz, 4 H); 7.49 (m, 6H); 7.20 (m, 6 H); 7.13 (m, 6 H); 6.98 (8 H +toluene); 6.77 (d, J=11.6Hz, 1 H); 6.55 (m, 2 H) ; 6.4 (m, 4 H); 6.02 (m, 1 H); 2.09 (toluene).¹³C NMR (100 MHz, CD₂Cl₂): δ179.6 (d, J=7.5 Hz), 168.9, 148.0 (d, J=45.1Hz), 144.6, 140.8, 138.3 (d, J=2.7 Hz), 137.0, 134.8, 134.5 (d, J=10.6Hz), 133.8, 131.8, 131.3, 130.5, 130.2, 130.0 (d, J=1.9 Hz), 129.3,128.5, 128.1 (d, J=9.8 Hz), 127.7, 127.0, 125.6, 125.2, 124.9 (d, 1.9Hz), 122.0, 121.2, 121.1, 120.5, 21.5. ³¹p NMR (162 MHz, C₆D₆): δ29.03.Anal. Calcd for C₄₉H₃₈NOPNi.0.33 toluene : C, 79.3; H, 5.27; N, 1.80.Found: C, 79.24; H, 5.37; N, 1.77.

EXAMPLE 28

[0161]2-(2-Methyl-6-trifluoromethylanilino)tropone Ni Complex: Thegeneral procedure was employed with 192 mg (0.51 mmol) of the sodiumsalt and 357 mg (0.51 mmol) of (Ph₃P)₂Ni(Ph) (Cl) to afford 205 mg (59%)of the desired complex as a yellow-orange solid. ¹H NMR (400 MHz,CD₂C1₂): δ7.49 (m, 6 H); 7.37 (m, 3 H); 7.27 (m, 7 H); 7.04 (d, J=9.9Hz, 1 H); 6.96 (m, 2 H); 6.86 (m, 2 H); 6.63 (d, J=10.6 Hz, 1 H); 6.55(m, 2 H.); 6.17 (m, 3 H); 6.05 (m, 1 H); 2.17 (s, 3 H). ¹³C NMR (100MHz, CD₂Cl₂) : spectrum is difficult to interpret due to extensive Fcoupling; δ180.1 (d, J =7.3 Hz), 168.0, 149.4 (d, J=46.0 Hz), 146.4,138.1, 136.8, 135.2, 134.8, 134.6 (d, J=10.6 Hz), 134.4, 134.0, 131.8,131.3, 130.1 (d J=2.5 Hz), 128.2 (d, J=9.7 Hz), 126.2, 125.1 (broad),124.8, 124.7 (broad), 124.5 (q, J=5.6 Hz), 124.3, 123.5, 122.4, 121.9,121.1, 118.9, 18.2. ³¹p NMR (162 MHz, CD₂Cl₂) : δ29.37. Anal. Calcd for:C, 69.25; H, 4.62; N, 2.07. Found C₃₉H₃₁NOPNiF₃: C, 69.15; H, 4.57; N,2.10.

EXAMPLE 29

[0162]2-(2,6-Dichloroanilino)tropone Ni Complex: The general procedurewas employed with 200 mg (0.50 mmol) of the sodium salt and 344 mg (0.50mmol) of (Ph₃P)₂Ni(Ph) (Cl) to afford 250 mg (75%) of the desiredcomplex as a yellow-orange solid. ¹H NMR (400 MHz, C₆D₆) : δ7.54 (m, 6H) ; 7.39 (m, 3 H); 7.29 (m, 6 H); 7.09 (dt, J=1.0, 10.2 Hz, 1 H); 6.96(m, 5 H); 6.72 (d, J=10.8 Hz, 1 H); 6.70 (d, J=8.1 Hz, 1 H); 6.63 (at,J=9.5 Hz, 1 H); 6.23 (at, J=9.5 Hz, 1 H); 6.23 (m, 2 H) ; 6.14 (m, 2 H).¹³C NMR (100 MHz, CD₂Cl₂): δ180.2 (d, J=6.8 Hz), 167.7, 149.9 (d, J=45.3Hz), 144.2, 137.1 (d, J=1.7 Hz), 135.5, 134.8, 134.7 (d, J=10.6 Hz),131.7, 131.3, 130.2 (d, J=2 Hz), 128.2 (d, J=9.7 Hz), 128.1, 125.6,124.9 (d, J=2.1 Hz), 123.2, 122.9, 121.4, 117.8. ³¹p NMR (162 MHz,CD₂Cl₂): δ29.13. Anal. Calcd for C₃₇H₂₈NOPNiCl₂: C, 67.00; H, 4.26; N,2.11. Found: C, 66.95; H, 4.37; N, 2.15.

EXAMPLE 30

[0163]2-(2,6-Dibromoanilino)tropone Ni Complex: The general procedurewas employed with 220 mg (0.49 mmol) of the sodium salt and 341 mg (0.49mmol) of (Ph₃P)₂Ni(Ph) (Cl) to afford 315 mg (85%) of the desiredcomplex as a yellow-orange solid. ¹H NMR (400 MHz, CD₂Cl₂) : δ7.54 (m, 6H) ; 7.39 (m, 3 H); 7.28 (m, 6 H); 7.21 (d, J=8.0 Hz, 2 H); 7.09 (m, 1H); 7.00 (m, 2 H); 6.94 (d, J=10.4 Hz, 1 H); 6.72 (d, J=10.8 Hz, 1 H);6.63 (at, J=9.4 Hz, 1 H); 6.56 (t, J=8.0 Hz, 1 H); 6.22 (m, 2 H); 6.14(t, J=7.2 Hz, 2 H). ¹³C NMR (100 MHz, CD₂C₂): δ180.2 (d, J=6.8 Hz),167.3, 149.6 (d, J=45.7 Hz), 146.5, 137.4, 135.5, 134.8, 134.7 (d,J=10.6 Hz), 132.0, 131.7, 131.3, 130.2 (d, J=1.6 Hz), 128.2 (d, J =9.8Hz), 126.4, 124.9 (d, J=2 Hz), 123.2, 123.0, 122.3, 121.4, 118.0. ³¹pNMR (162 MHz, CD₂Cl₂) : δ29.03. Anal. Calcd for C₃₇H₂₈NOPNiBr₂: C,59.08; H, 3.75; N, 1.86. Found: C, 59.35; H, 3.82; N, 1.90.

EXAMPLE 31

[0164]2-(2-Methylanilino)tropone Ni Complex: The general procedure wasemployed with 100 mg (0.34 mmol) of the sodium salt and 234 mg (0.34mmol) of (Ph₃P)₂Ni(Ph) (Cl) to afford 105 mg (51%) of the desiredcomplex as a yellow-orange solid. ¹H NMR (400 MHz, CD₂Cl₂): δ7.50 (m, 6H); 7.39 (m, 3 H); 7.28 (m, 6 H); 6.98 (dt, J=1.0, 10.2 Hz, 1 H);6.87-6.67 (m, 6 H); 6.59 (d, J=10.4 Hz, 1 H); 6.53 (dd, J=1.3, 7.6 Hz, 1H); 6.49 (at, J=9.5 Hz, 1 H); 6.27 (d, J=11.6 Hz, 1 H); 6.18 (m, 2 H);6.06 (bs, 1 H); 2.19 (s, 3 H) ¹³C NMR (100 MHz, CD₂Cl₂): δ179.9 (d,J=7.5 Hz), 168.5, 151.6 (d, J=44.4 Hz), 147.8, 138.0 (broad), 137.1(broad), 134.7, 134.6 (d, J=10.6 Hz), 134.1, 132.1, 131.9, 131.5, 130.1(d, J=2.3 Hz), 130.0, 128.2 (d, J=9.7 Hz), 126.3, 126.2, 125.0 (broad),124.2, 122.0, 121.0, 120.8, 118.6, 17.9. ³¹p NMR (162 MHz, CD₂Cl₂): 629.43. Anal. Calcd for C₃₈H₃₂NOPNi: C, 75.02; H, 5.30; N, 2.30. Found:C, 74.12; H, 5.33; N, 2.31.

EXAMPLE 32

[0165]2-(2,3,4,5,6-Pentafluoroanilino)tropone Ni Complex: The generalprocedure was employed with 136 mg (0.44 mmol) of the sodium salt and308 mg (0.44 mmol) of (Ph₃P)₂Ni (Ph) (Cl) to afford 169 mg (57%) of thedesired complex as a yellow-orange solid. ¹H NMR (400 MHz, CD₂Cl₂) :δ7.52 (m, 6 H); 7.39 (m, 3 H); 7.30 (m, 6 H); 7.18 (dt, J=0.9, 10.25 Hz,1 H); 7.06 (m, 1 H); 6.87 (d, J=7.2 Hz, 2 H); 6.80 (d, J=10.8 Hz, 1 H);6.74 (at, J=9.6 Hz, 1 H); 6.50 (d, J=11.2 Hz, 1 H) ; 6.36 (t, J=7.15 Hz,1 H); 6.28 (m, 2 H). ¹³C NMR (100 MHz, CD₂Cl₂) : spectrum difficult tointerpret due to extensive F coupling. δ180.8 (d, J=6.5 Hz), 169.1,152.2 (d, J=45.5 Hz), 136.8, 136.2, 135.4, 134.6 (d, J=10.7 Hz), 132.3(m), 131.4, 131.0, 130.3 (d, J=1.9 Hz), 128.9 (m), 128.3 (d, J=9.8 Hz),125.5 (d, J=2.5 Hz), 124.5, 124.3, 122.0, 118.0. ³¹p NMR (162 MHz,CD₂Cl₂) : δ29.71. ¹⁹F NMR (377 MHz, CD₂Cl₂): 6-147.73 (m), -163.75 (t,J=22.6 Hz), −166.52 (m). Anal. Calcd for C₃₇H₂₅NOPNiF₅: C, 64.94; H,3.68; N, 2.05. Found: C, 64.45; H, 3.90; N, 2.31.

EXAMPLE 33

[0166] Bistropone Ni Complex from 2-(2,6-diisopropylanilino)-tropone: Toa flame dried Schlenk flask in a glovebox were added the sodium salt ofthe 2-anilinotroponee. THF (377 mg, 0.90 mmol)) and (DME)NiBr₂ (139 mg,0.45 mmol). The flask was removed form the glovebox and placed on avacuum line under Ar. Et₂O (20 mL) was added to the flask, and thereaction was allowed to stir at room temperature for 15 h. The crudereaction mixture was filtered through filter paper and condensed toproduce 240 mg (88%) of a red-brown solid. ¹H NMR (400 MHz, C₆D₆) :δ7.29-7.21 (m, 6 H); 6.26-6.18 (m, 8 H); 5.92 (m, 2 H); 4.18 (sept,J=6.8 Hz, 4 H); 1.74 (d, J=6.8 Hz, 12 H); 1.19 (d, J=6.8 Hz, 12 H). ¹³CNMR (100 MHz, C₆D₆): 6 180.4, 168.9, 143.6, 141.1, 134.6, 133.8, 126.7,124.0, 122.8, 120.7, 119.3, 29.2, 24.5, 24.1. Anal. Calcd forC₃₈H₄₂N₂O₂Ni: C, 73.67; H, 7.16; N, 4.50. Found: C, 74.10; H, 7.25; N,4.39.

EXAMPLES 34-40 Polymerizations of Ethylene with (VIII)

[0167] A 1000 mL Parr® autoclave was heated under vacuum up to 110° C.,was cooled, and was backfilled with ethylene. The autoclave was chargedwith toluene (190 mL), was degassed with ethylene (3×1.38 MPa), and waspressurized with ethylene to 2.76 MPa for the reaction. The stirringmotor was engaged, and the reactor was allowed to equilibrate at thedesired temperature for 10 min. In a glove box, a Schlenk flask wascharged with the catalyst. The Schlenk flask was removed from the glovebox and was placed on a vacuum line under Ar. The catalyst was dissolvedin toluene (10 mL) and was cannula transferred into the autoclave whichhad been vented. The autoclave was sealed and was pressurized to 2.76MPa. At the appropriate time, the reactor was vented, and the polymerwas isolated via filtration and was dried in a vacuum oven. Variationsin time, temperature, solvent, and catalyst loading were employed togenerate the data in Table 2.

EXAMPLES 41-80

[0168] Unless otherwise noted, the “catalyst” (Ni compound) was (VIII).General Procedure for High Pressure (Above Atmospheric) EthylenePolymerizations. A 1000 mL Parr autoclave was heated under vacuum up to110° C. and then was cooled to the desired reaction temperature andbackfilled with ethylene. The autoclave was charged with solvent (190mL), degassed with ethylene (2×1.38 MPa), and pressurized with ethyleneto,1.38 MPa. The stirring motor was engaged, and the reactor allowed toequilibrate at the desired temperature for approximately 10 min. In aglovebox, a side arm flask was charged with the catalyst. The flask wasremoved from the glovebox and placed on a vacuum line under Ar. Thecatalyst was dissolved in 10 mL toluene and cannula transferred into thevented autoclave with stirring motor off. The autoclave was sealed andpressurized to the desired level, and the stirring motor was reengaged.After the prescribed reaction time, the stirring motor was stopped, thereactor was vented, and the polymer isolated via precipitation frommethanol and dried in a vacuum oven. This procedure was employed withmodifications in time, temperature, ethylene pressure, and solvent. Forthe additive studies, 170 mL of toluene and 20 mL of the respectiveadditive were used in place of the 190 mL toluene mentioned above. Forthe studies with excess PPh₃, both the catalyst and PPh₃ were added inthe same 10 mL toluene.

[0169] Procedure for Ethylene Polymerization at 1 atm. In a glovebox, aside arm flask was charged with the catalyst (7.6 μmol). The flask wasremoved from the glovebox and placed on a vacuum line under argon.Toluene (40 mL) was added to flask, and the flask was placed in an 80°C. oil bath. After 10 min, the flask was evacuated and backfilled withethylene 3 times and left open to ethylene for the duration of thepolymerization. After 2 h, the reaction was cooled to RT and poured into200 mL stirred MeOH. After stirring 12 h, an oil had separated out onthe bottom. The solvent was decanted and the residual oil dissolved inhexane. This solution was filtered through a pad of silica gel withadditional hexane, and the solvent was removed in vacuo to yieldpolymer.

[0170] Some of these polymerization runs are reported under differentexample numbers in the tables. They are repeated to illustrate theeffect of different variables on the polymerization. Table 3 shows theeffect of temperature, Table 4 the effect of ethylene pressure, Table 5the effect of catalyst loading, Table 6 the effect of various additives,and Table 7 the effect of various solvents. Table 8 shows the effect ofvarying the substitution on the phenyl ring derived from the aniline andthe column labeled “Ar” gives that substitution pattern.

EXAMPLES 81-82 1-Hexene Polymerizations with (VIII)

[0171] A Schlenk flask in a glove box was charged with the catalyst. Theflask was removed from the glove box and was placed on a vacuum lineunder Ar. Toluene and 1-hexene were added to a separate flask, and theflask was placed in an oil bath at the appropriate temperature and wasallowed to equilibrate for 10 min. The catalyst was dissolved in toluene(0.50 mL) and was cannula transferred into the toluene/1-hexenesolution. The solution was allowed to stir for the prescribed time, andthe solvent and excess 1-hexene were removed to yield the crude polymer.Further purification was effected via filtration of a hexane solution ofthe polymer through a pad of Celite® and removal of the solvent invacuo. These conditions were used to generate the data in Table 9. TABLE2 mol cat temp time Yield branches/ T_(m) Ex. (× 10⁶) Solvent (° C.) (h)(g) TON^(a) M_(n) PDI 1000 carbons (° C.) 14 3.0 Toluene 40 1.0 0.1251490 68000 3.57 14 121 15 3.0 Toluene 60 1.0 0.740 8800 151000 2.39 29102 16 3.0 Toluene 80 1.0 1.14 13600 101000 1.98 48 82 17 10.0 Toluene40 1.0 1.615 5770 186000 3.67 10 124 18 14.8 Toluene  60^(b) 0.5 13.6633000 57000 2.80 64 87 19 6.0 CH₂Cl₂ 40 1.0 0.312 1857 86000 4.04 — 11620 7.6 Hexane 40 1.0 0.527 2480 112000 3.92 — 122

[0172] TABLE 3^(a) temp yield Branches per Ex. (° C.) (g) TON^(b) M_(n)PDI 1000 carbons 41 40 1.20 8240 203946 2.81 8 42 60 6.78 31900 2922151.97 27 43 80 11.41 53600 118962 1.75 49 44 100 4.04 19000 60714 1.85 67

[0173] TABLE 4 ethylene yield Branches per Ex. (MPa) (g) TON^(b) M_(n)PDI 1000 carbons 45^(c)  14 0.145 980 6700 2.03 113 46  50 4.0 2700049774 1.68 90 47 100 6.3 42500 62485 1.89 76 48 200 9.2 62120 89637 1.8461 49  200^(d) 7.63 52400 91500 1.84 61 50 400 7.1 47800 103908 1.95 4551 600 2.6 17500 119571 1.97 41

[0174] TABLE 5^(a) mol cat yield Branches per T_(m) Ex. (× 10⁶) (g)TON^(b) M_(n) PDI 1000 carbons (° C.) 52 3.0 0.74 8800 151000 2.39 29102 53 7.6 6.78 31900 292215 1.97 27 54^(c) 14.8 13.66 33000 57000 2.8064 87

[0175] TABLE 6 additive yield Branches per Ex. Solvent (mL) (g) TON^(b)M_(n) PDI 1000 carbons 55 Toluene none 2.82 19000 189000 1.81 37 56Toluene EtOAc 2.28 15700 192000 1.80 36 (1) 57 Toluene H₂O(1) 1.40 9600128000 1.85 38 58 Hexane H₂O(1) 1.48 10200 135000 1.89 39 59 TolueneEtOH 1.12 7700 131000 1.88 37 (1) 60 Toluene NEt₃(1) 2.74 18800 1460002.02 38 61 Toluene EtOAc 3.82 26200 163000 1.92 43 (20) 62 Toluene H₂O0.850 5800 86000 2.31 41 (20) 63 Toluene EtOH 0.160 1100 21000 2.35 48(20) 64 Toluene NEt₃ 0.720 5000 87000 1.54 37 (20)

[0176] TABLE 7 yield branches per Ex. solvent (g) TON^(b) M_(n) PDI 1000carbons 65 toluene 2.82 19000 189000 1.81 37 66 THF 3.34 22500 1460001.81 39 67 hexane 2.59 17400 163000 1.79 35 68 PhCl 4.78 32200 1820001.90 46 69 PhCl^(b) 8.82 59300 71300 2.08 67 70 EtOAc 0.340 2290 660004.01 33

[0177] TABLE 8^(a) Yield Branches per Ex. Ar (g) TON^(b) M_(n) PDI 1000carbons 71 2,6-di-i-Pr 7.63 52400 91500 1.84 61 72 2,6-diMe 4.74 3260042400 1.74 61 73 2-CH₃-6-CF₃ 6.0 41200 87900 1.94 59 74 2,6-diPh 8.7059800 94900 1.77 53 75 2,6-diCl 3.40 23400   10000^(c) 1.96 53 762,6-diBr 3.46 23800 22300 1.93 56 77 2-t-Bu-6-CH₃ 0.880 6000 115000 2.02 73 78 2-t-Bu Trace 17600 2.13 72 79 2-CH₃ 0.810? 5600   4700^(b)2.41 57 80 pentafluoro 1.02? 7000   1570^(b) 3.03 49

[0178] TABLE 9 Ex. mol cat (× 10⁶) Solvent^(a) 1-Hexene (vol %) Temp (°C.) time (h) yield (mg) TO DP branches/1000 carbons 81 7.6 Toluene 50 403 84 130 21 147 82 7.6 Toluene 50 60 3 127 200 16 152

[0179]

[0180] To separate flame dried Schlenk flasks in a glove box were addedthe sodium salt of 2-(2,6-di-i-propylanilino)troponee. THF made inExample 12 (375 mg, 1.0 mmol), and (TMEDA)Ni(Ph)(Cl) [see E. Wenschub,Z. Chem., vol. 27, p. 448 (1987)] (286 mg, 1.0 mmol). Both flasks wereremoved from the glove box and placed on a vacuum line under Ar. Toluene(10 mL) was added to each flask, and the flask containing(TMEDA)Ni(Ph)(Cl) was cooled to −40° C (acetone/dry ice bath). Thetoluene solution of the ligand salt was slowly cannula transferred intothe precooled flask (10 min). After complete transfer (washed with 5 mLtoluene), the reaction was maintained at −40° C. for 2 h and thenallowed to warm to RT over one h. The reaction mixture was cannulatransferred onto a pad of Celite® and filtered under Ar. The Celite padwas washed with toluene (2×10 mL), and the solvent volume was reduced invacuo to 10 mL. Pentane (50 mL) was added, and the Schlenk flask wasplaced in a −30° C. freezer overnight. Solvent was removed from theprecipitate via cannula filtration, and the residual solid was washedwith pentane (3×5 mL). Drying in vacuo produced 150 mg (30%) of anorange solid. ¹H NMR (400 MHz, C₆D₆) : δ8.52 (dd, J=6.6, 1.6 Hz, 2 H);7.32 (dd, J=8.0, 1.2 Hz, 2 H); 7.07 (m, 4 H); 6.76 (t, J=7.2 Hz, 2 H);6.67 (m, 2 H); 6.47 (tt, J=7.6, 1.6 Hz, 1 H); 6.37 (d, J=11.5 Hz, 1 H);6.27 (ddd, J=11.6, 8.8, 1.2 Hz, 1 H); 6.13 (t, J=9.4 Hz, 1 H); 6.07 (m,2 H); 3.29 (sept, J=6.8 Hz, 2 H); 1.39 (d, J=6.8 Hz, 6 H); 1.10 (d,J=6.8 Hz, 6 H). ¹³C NMR (100 MHz, C₆D₆) 6 179.8, 170.5, 152.6, 152.2,144.6, 142.7, 137.1, 136.0, 134.8, 132.8, 126.3, 125.1, 123.9, 123.3,122.4, 122.1, 121.5, 120.5, 28.8, 25.5, 23.7.

[0181] To a flame dried Schlenk flask in a glovebox were added thesodium salt of 2-(2,6-di-i-propylanilino)tropone. THF (500 mg, 1.33mmol) and (TMEDA)Ni(Ph)(Cl) (381 mg, 1.33 mmol). The flask was removedfrom the glovebox, was placed on a vacuum line under Ar, and was cooledwith an ice water bath. Toluene (25 mL) and CH₃CN (1.5 mL) were added tothe flask, which was removed from the ice water bath after 30 min. Thereaction was allowed to stir at ambient temperature for 14.5 h. Initialcannula filtration of the solution was followed by cannula transfer ontoa pad of Celite and filtration under Ar. The Celite® pad was washed withtoluene (20 mL), and the solvent volume was reduced in vacuo to 5 mL.Pentane (50 mL) was added, and the Schlenk flask was placed in a −30° C.freezer overnight. Solvent was removed from the precipitate via cannulafiltration, and the residual solid was washed with pentane (5 mL).Drying in vacuo produced 90 mg (11%) of a red-brown solid. ¹H NMR (400MHz, C₆D₆) : δ7.21-7.29 (m, 6 H); 6.18-6.26 (m, 8 H); 5.92 (m, 2 H);4.18 (sept, J=6.8 Hz, 4 H); 1.74 (d, J=6.8 Hz, 12 H); 1.19 (d, J=6.8 Hz,12 H).

What is claimed is:
 1. A process for the polymerization of olefins,comprising the step of contacting, at a temperature of about −100° C. toabout +200° C., one or more olefins with an active catalyst comprising anickel complex of an anion of the formula

wherein: R² is hydrocarbyl or substituted hydrocarbyl, provided that R²is attached to said nitrogen atom in (I) by an atom that has at least 2other atoms that are not hydrogen attached to it; and R³, R⁴, R⁵, R⁶ andR⁷ are each independently hydrogen, hydrocarbyl, substituted hydrocarbylor a functional group, provided that any two of R³, R⁴, R⁵, R⁶ and R⁷vicinal to one another may form a ring.
 2. The process as recited inclaim 1 wherein the olefin is selected from the group consisting ofcyclopentene, a styrene, a norbornene, and compounds of the formula R¹⁷CH═CH₂, wherein R¹⁷ is hydrogen or alkyl.
 3. The process as recited inclaim 2 wherein the olefin is a compound of the formula R¹⁷CH═CH₂. 4.The process as recited in claim 1 wherein said nickel complex is

wherein: L¹ is a monodentate monoanionic ligand into which an olefinmolecule may insert between L¹ and the nickel atom, and L² is an emptycoordination site or a monodentate neutral ligand which may be displacedby an olefin, or L^(1 l L) ² taken together are a monoanionic bidentateligand into which an olefin may insert between said monoanionicbidentate ligand and said nickel atom; and provided that when L¹ and L²taken together are

then a cocatalyst is also present.
 5. The process as recited in claim 4wherein L¹ and L² taken together are not (I).
 6. The process as recitedin claim 5 wherein the olefin is selected from the group consisting ofcyclopentene, a styrene, a norbornene and compounds of the formulasR¹⁷CH═CH₂, wherein R¹⁷ is hydrogen or alkyl.
 7. The process as recitedin claim 6 wherein the olefin is a compound of the formula R¹⁷CH═CH₂. 8.The process as recited in claim 1 wherein R² is

wherein R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any two of R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ vicinal to one another takentogether may form a ring.
 9. The process as recited in claim 5 whereinR² is

wherein R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any two of R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ vicinal to one another takentogether may form a ring.
 10. The process as recited in claim 9 whereinR¹¹ and R¹⁵ are each independently chosen from the group consisting ofalkyl containing 1 to 6 carbon atoms, perfluoroalkyl, alkoxy, phenyl andhalo.
 11. The process as recited in claim 10 wherein R¹², R¹³ and R¹⁴are hydrogen.
 12. A compound of the formula

wherein: R² is hydrocarbyl or substituted hydrocarbyl, provided that R²is attached to said nitrogen atom in (I) by an atom that has at least 2other atoms that are not hydrogen attached to it; and R³, R⁴, R⁵, R⁶ andR⁷ are each independently hydrogen, hydrocarbyl, substituted hydrocarbylor a functional group, provided that any two of R³, R⁴, R⁵, R⁶ and R⁷vicinal to one another may form a ring; L¹ is a monodentate monoanionicligand and L² is a monodentate neutral ligand or an empty coordinationsite, or L¹ and L² taken together are a monoanionic bidentate ligand.13. The compound as recited in claim 12 wherein R² is

wherein R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any two of R¹¹ , R¹², R¹³, R¹⁴ and R¹⁵ vicinal to one another takentogether may form a ring.
 14. The compound as recited in claim 13wherein R¹¹ and R¹⁵ are each independently chosen from the groupconsisting of alkyl containing 1 to 6 carbon atoms, perfluoroalkyl,alkoxy, phenyl and halo.
 15. The compound as recited in claim 14 whereinR¹², R¹³ and R¹⁴ are hydrogen.
 16. A process for making a 2-arylaminosubstituted tropone, comprising the step of contacting, in solution at atemperature of about 20° C. to about 150° C., a first compound of theformula

a second compound of the formula HNR⁹R¹⁹ (IV), a palladium compound, abase capable of deprotonating said second compound, and a third compoundwhich is a mono- or diphosphine in which all of the bonds to phosphorousare to carbon atoms, wherein: R³, R⁴, R⁵, R⁶ and R⁷ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl or afunctional group, provided that any two of R³, R⁴, R⁵, R⁶ and R⁷ vicinalto one another may form a ring; R⁸ is a group such that the conjugateacid of −OR⁸ has a pKa of <0 in water at 20° C.; R¹⁹ is hydrocarbyl,substituted hydrocarbyl or hydrogen; and R⁹ is aryl or substituted aryl.17. A compound of the formula

wherein: R³, R⁴, R⁵, R⁶ and R⁷ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any two of R³, R⁴, R⁵, R⁶ and R⁷ vicinal to one another may form aring; and each of R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any two of R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ vicinal to one another takentogether may form a ring; provided that: both of R¹¹ and R¹⁵ are nothydrogen; and/or the total of the Hammett a constants for R¹¹, R ¹²,R¹³, R¹⁴ and R¹⁵ is about 0.50 or more; and/or an E_(s) for one or bothof R¹¹ and R¹⁵ is −0.10 or less.
 18. An anion of the formula

wherein: R² is hydrocarbyl or substituted hydrocarbyl, provided that R²is attached to said nitrogen atom in (I) by an atom that has at least 2other atoms that are not hydrogen attached to it; and R³, R⁴, R⁵, R⁶ andR⁷ are each independently hydrogen, hydrocarbyl, substituted hydrocarbylor a functional group, provided that any two of R³, R⁴, R⁵, R⁶ and R⁷vicinal to one another may form a ring.
 19. The anion as recited inclaim 18 wherein R² is

wherein R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are each independently hydrogen,hydrocarbyl substituted hydrocarbyl or a functional group, provided thatany two of R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ vicinal to one another takentogether may form a ring.
 20. The anion as recited in claim 19 whereinR¹¹ and R¹⁵ are each independently chosen from the group consisting ofalkyl containing 1 to 6 carbon atoms, perfluoroalkyl, alkoxy, phenyl andhalo.
 21. The anion as recited in claim 20 wherein R¹², R¹³ and R¹⁴ arehydrogen.
 22. The anion as recited in claim 19 wherein R³, R⁴, R⁵, R⁶,and R⁷ are hydrogen.